JPH02851A - Photographic film antistatic lined layer having auxiliary layer with improved characteristic - Google Patents

Abstract

PURPOSE: To improve the processing property by coating an antistatic layer with an auxiliary layer essentially comprising a conductive polymer and a crosslinking agent dispersed in a gelatin. CONSTITUTION: This film consists of a silver halide layer on one surface of a base body and an antistatic layer applied on the other surface of the base body. The antistatic layer is coated with an auxiliary layer essentially comprising a crosslinkable conductive polymer having carboxylic acid groups bonded to act as functional groups and a crosslinking agent for the conductive polymer dispersed in a gelatin. The auxiliary layer shows 3 to 12pH. The antistatic property of the antistatic layer is obtd. through the auxiliary layer. Thereby, the obtd. auxiliary rear coating layer has improved processing property.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention is based on U.S. Pat. is related to. The invention is also disclosed in U.S. Pat. No. 4,701,403 to Miller, granted October 20, 1987;
It also pertains to the "Two-Layer Method for Applying Antistatic Compositions to Polyester Supports," which is a two-layer method for applying a thin, transparent antistatic layer to photographic films.
method oriented. The present invention provides an auxiliary layer designed to be deposited on top of such a layer.

INDUSTRIAL APPLICATION FIELD OF THE INVENTION The present invention relates to photographic films, and more particularly to an improved auxiliary backing for such films, which is capable of directing antistatic properties from the antistatic subbing layer to the outside of the film surface. The present invention relates to a photographic film having a thin layer.

BACKGROUND OF THE INVENTION The tendency of polymeric film supports for photographic films to accumulate electrostatic charge is well known. This is especially a problem when the film is designed to be machine processed and different sides are processed rapidly. The electrostatic charge generated at this time sensitizes the photographic layer or layers to which it is applied.
K cannot easily overlook this.

In order to prevent the accumulation of these electrostatic charges, it has been well known to use a so-called antistatic layer. 5c
Hadt, U.S. Pat. No. 4,225,665 (1
) a water-soluble copolymer of a sodium salt of styrene sulfonic acid and a monomer containing carboxyl groups; (2) a hydrophilic polymer containing carboxyl groups; and (3) a mixture of a water-soluble polyfunctional aziridine. It states one thing.

When this mixture is applied in a single layer over, for example, resin-primed poly(ethylene terephthalate), it provides excellent protection against #1 charge build-up (eg, surface resistance).

Miller, U.S. Pat. No. 4,701,403, describes an improvement on the aforementioned 5chadt patent, in which a polymer, such as component (1), optionally comprises a composition comprising component (2). The product is applied to the support in a first coat and, after drying, the aziridine component (6) is applied as a second coating following this. This improved method allows an improved thinner antistatic layer to be applied without premature reaction of the aziridine with other ingredients. The products of such premature reactions sometimes clog coating equipment, create a messy mess, and are industrially unacceptable.

US Pat. No. 4,585,730 to Cho describes an auxiliary layer comprising a conductive polymer as described therein. This layer is advantageous in its antistatic properties to transfer charge from the basecoat layer to the surface. However, the layers described in this patent often suffer from certain disadvantages, such as problems with sticking and poor processability in the liquids in which the photographic layers are processed.

It would therefore be desirable to provide an improved auxiliary layer to coat the antistatic layer of a photographic film that is effective in imparting antistatic properties to the surface. Such layers also serve as backing layers for photographic films containing antistatic layers. It is desirable to provide such an auxiliary layer that has good adhesion to already applied layers and is stable in photographic processing solutions.

SUMMARY OF THE INVENTION According to the present invention, the present invention comprises a support, at least one silver halide deposited on one side of the support, and an antistatic agent deposited on the opposite side of the support, The antistatic layer consists essentially of at least one crosslinkable conductive polymer having functionally bonded carboxylic acid groups and a crosslinking agent for the conductive polymer dispersed in gelatin. A photographic film is provided, characterized in that an auxiliary layer of from 3 to 12 times is deposited, the antistatic properties of the antistatic layer being conducted through this auxiliary layer.

DETAILED DESCRIPTION OF THE INVENTION The term "essentially consisting" as used in the claims does not exclude unspecified components or conditions that do not affect the characteristics of the invention.

The crosslinkable conductive polymer can be present alone or in combination with at least one other crosslinkable conductive polymer. A particularly preferred crosslinkable conductive polymer is poly(sodium styrene sulfonate-maleic anhydride). Other crosslinkable conductive polymers include hexadecyl betaine, 01-
12 alkyl groups such as alkyldimethylbetaine, carboxylated imidazoline, and cocoamidoitaine. These conductive polymers containing functionally bonded carboxylic acid groups are
~30 shield f1% range, preferably 1.5-2.5 heavy i
t% can be added to the auxiliary layer of the invention. The term "gelatin binder" refers to a binder whose major component is gelatin. Polyvinyl alcohol, dextrin, heptulose derivative, modified gelatin,
Gelatin substitutes such as water-soluble acrylic latex and the like can be present in amounts such as, for example, up to 17% by weight.

Crosslinking agents useful within the scope of the present invention include polyfunctional aziridines, such as those described in 5chadt, U.S. Pat. No. 4,225,665 and Miller, U.S. Pat. is included. I will discuss this here with reference to the description regarding aziridine.

Other useful crosslinking (curing) agents include chromium alum, carbodiimides, isoxazolinicum salts, and the like.

Particularly preferred is the ink erythritol-trivator (2-methylaziridine) added to the gelatin binder. The crosslinking agent is 0.5 to 5 of the gelatin binder.
．． It may be present in an amount of 0%, preferably between 2.0% and 0%.

The mixture of gelatin binder, crosslinkable conductive polymer and crosslinker in water of the present invention is made prior to application.

Other additives may also be present in the mixture, such as antihalation dyes, surfactants, wetting agents and hardening agents. At this point just before application, the - of the liquid is 6~
12, preferably 6-8.

Although the aqueous coating compositions made as described above can be successfully applied to any conventional photographic film support, the preferred supports are primed with a conventional resin layer or layers. poly(ethylene terephthalate), on one side of which is deposited a photographically sensitive layer, preferably a silver halide emulsion layer, and on the other side a layer of an antistatic composition, e.g. His US Patent No. 4,
No. 225,665, Miller U.S. Patent No. 4.7
A backing layer of an antistatic coating such as No. 01,403 is applied. Although the present invention is not limited to any particular antistatic coating, the antistatic coatings of Miller, U.S. Pat.
(See column 56, line 56 to 4th column, line 56, the descriptions are listed here for reference) are preferred. A backing layer of the present invention is applied on top of this antistatic layer with a thickness of about 30 to 901 R9/dm2.
It is preferably applied at a coverage of about 40 to 60 Q/dm2.

Thus, in a particularly preferred embodiment, the present invention provides a method of applying a gelatin undercoat on both sides of preferably dimensionally stable polyethylene terephthalate, suitably primed with a conventional resin undercoat thin adhesion primer. A photographic film consisting of a support that may have a sublayer applied to it. A standard silver halide emulsion layer is applied on one side of the support, and the skin is then overcoated with a protective overcoat layer, such as a conventional hardened gelatin abrasion layer. The opposite side of the emulsion layer is preferably provided with the antistatic layer of Miller, US Pat. No. 4,701,403, followed by the auxiliary layer of the present invention. This layer of the present invention can be an antihalation layer or can be applied as simply a gelatin anticurl layer, which is well known to those of ordinary skill in the art.

In one embodiment, the auxiliary layer can be two separately deposited layers, each layer comprising gelatin, one layer comprising at least one crosslinkable conductive polymer, and the other layer contains a crosslinking agent, both of which are those mentioned above. For example, a conductive polymer dispersed in gelatin is deposited first, followed by gelatin and a crosslinking agent. Upon wetting, the crosslinking agent migrates into the conductive polymer-containing chamber, effectively causing gelatin and polymer crosslinking to take place as described above.

Many advantages are obtained when the skin of the present invention is made as described herein. First, this layer provides the desired transfer of antistatic properties from the antistatic layer to the film surface. Second, the layers of the present invention are stable and, once decomposed, will withstand extremely harsh photographic processing. This is highly desirable since previously known layers tended to flake off during the processing process. Loss of layer integrity is a drawback that cannot be overlooked as layer granules tend to contaminate the processing solution and, more importantly, result in a loss of antistatic property transfer. That's why. In addition, the adhesion between the layers already applied or the layers to be applied subsequently is enhanced by the presence of the layers of the invention compared to those known to date. This indicates that a layer very similar to the one described here, which has the required hardening properties from gelatin hardeners and others, and which also has a satisfactory transfer of antistatic properties, does not exhibit the properties described above. This is a surprising result.

It is theorized that crosslinking agents such as, but not limited to those described above, react internally with gelatin, conductive polymers, and carboxyl groups on the surface of the antistatic subbing layer to provide good adhesion. However, it is surprising that the transfer of antistatic properties was preserved, since it was thought that conductive polymers must have all of the available groups on the polymer chain to provide transfer of antistatic properties. .

Many of the common photosensitive materials can be present as the emulsion layer described above. These include photopolymer diazo, cellular imaging materials, etc. This film is suitable for use in well-known imaging fields such as graphic arts, printing, medical, and information systems, among others.
It can also be used in misalignment. The photographic films of this invention are particularly useful in processes where they are rapidly transported and handled by machines, such as phototypesetting.

Particularly useful elements include, for example, so-called "luminescent" films that can be handled under relatively bright safe light.

EXAMPLE The following is a non-limiting example of the invention, in which percentages are by weight.

Examples 1 to 5 The solution for backing anti-shihalation layer was 1200. 15.5% gelatin in 15.5% distilled water at 149°C.
Made by mixing for minutes. Add this mixture to 38
℃, and added the following ingredients (manufactured by Niss Co., Ltd.) Ethyl alcohol 450.0 Distilled water 1050.0 SF yellow color (1), 4.7% aqueous solution 108.0 S-1240 dye (2.6. 0% aqueous solution,
. ,. . .

Acid violet dye (3), 1zo% aqueous solution
54.0 Polyethyl acrylate latex, 32.5% in water 54[10'' S-1240 dye (D781) ES40, manufactured by Henkel) Sodium hydroxide, 5N 18.0 (3) Acid violet dye (D720) (1 ) SF
Yellow (D782) These components were thoroughly mixed and then each
It was divided into parts i'. The following were further added to the six parts, processed and used in the examples: Crosslinker (1) Conductive Polymer Control 100 Control 2 Implementation of U.S. Pat. No. 4,585,730 N
Sample 3 of 1 (1) Solution of antaerythritol retriever-(2-methylazirizoin) propionate in distilled water.

(2) Poly(sodium styrene sulfonate-maleic anhydride) crosslinkable conductive polymer diluted with distilled water (approximately 3,000 servings per thousand on average as determined by known osmosis methods)
0).

Each sample of the above solution had a thickness of 0.004 inches (0.10
Both sides of the 101 liter were coated with resin 1 and pre-coated with an antistatic layer similar to the solution chamber 4 of Example 1 described in Miller's U.S. Pat. No. 4,701,403.
Deposited on polyethylene terephthalate film.

Each solution was deposited onto the antistatic layer described above to give a coating thickness of about 55 to dm2. After drying, the surface resistance of each layer was determined by Cho, US Pat. No. 4,585,750, Example 1, No. 44! It was measured according to the method described in Ill. With the exception of control A1, the prevention of charging was very good in all cases. Each sample was then processed through standard photographic processing equipment (developing, fixing, rinsing and drying) and the surface was inspected for electrostatic resistance and adhesion. In the case of Examples 1 to 5, it was observed that the resistance and adhesion were extremely good. None of the materials developed delamination during processing and all antistatic mobility was maintained. In the case of Funtrol 1 and 2, adhesion was poor and many of the layers delaminated during the processing process. Control 2 was worse in preventing charging than Examples 1 to 5.

Examples 6-19 The antihalation solutions of Examples 1-5 above were made in large quantities to demonstrate the effectiveness of other crosslinking agents and other conductive polymers or combinations of conductive polymers within the scope of the present invention. ,
It was divided into 14 pieces of 3040.9 each. The following items were added to each part: 12 Comparative Examples 10 19 Comparison Examples 10 (1) Cocoamide Betaine Alkaryl Chemicals product, trade name Alkateric C
AB (2) Each solution sample of the same conductive polymer as in Examples 1-5 above was applied to a film support with an antistatic layer as described in Examples 1-5. Each sample is from Example 1
-Tested for charging and adhesion as described in 5. In the case of the comparative examples (Examples 12 and 19), the antistatic properties were significantly lacking for both the samples before and after treatment, and the adhesion of the antihalation layer to the antistatic layer was poor. . Other examples (6-11 and 13-1
In 8), the antistatic property is good to very good, -
The one coated with -7 was also better than the one coated with No. 5. Adhesion was very good for all of these samples, indicating that other conductive polymers, alone or in combination, would function within the scope of the present invention. Although described above, the present invention can be further summarized and illustrated by the following embodiments.

1) consisting of a support, at least one silver halide emulsion deposited on one side of the support, and an antistatic agent deposited on the opposite side of the support; has an auxiliary layer consisting essentially of at least one crosslinkable conductive polymer having functionally attached carboxylic acid groups and a crosslinking agent for the conductive polymer dispersed in gelatin. , 3 to 12 states, wherein the antistatic properties of the antistatic layer are derived through this auxiliary layer.

2) The auxiliary layer consists of two gelatin-containing layers deposited separately, the first deposited layer comprising at least one crosslinkable conductive polymer, and the second deposited layer comprising a crosslinking agent. The photographic film described in the preceding item 1), which contains the following.

3) The crosslinkable conductive polymer is selected from the group consisting of poly(sodium styrene sulfone-maleic anhydride), hexadecyl betaine, alkyl dimethyl betaine, carboxylated imidazoline, cocoamido betaine, and mixtures thereof. The photographic film according to item 1) above.

4) The crosslinkable conductive polymer is selected from the group consisting of poly(sodium styrene sulfonate-maleic anhydride), hexadecyl betaine, alkyl dimethyl betaine, carboxylated imidazoline, cocoamido betaine, and mixtures thereof. Photographic film as described in the preceding paragraph.

5) The photographic film according to item 1 above, wherein the crosslinkable conductive polymer is present in an amount of 15 to 30% by weight (11% by weight) based on the weight of the gelatin binder.

6) The photographic film according to item 2), wherein the crosslinkable conductive polymer is present in an amount of 0.5 to 30% by weight based on the weight of the gelatin binder.

7) The photographic film according to item 1), wherein the crosslinking agent is selected from the group consisting of polyfunctional aziridine, chromium alum, carbodiimide, and isoxazolinium salt.

8) The photographic film according to item 2) above, wherein the crosslinking agent is selected from the group consisting of polyfunctional aziridine, chromium alum, carbodiimide, and isoxazolinium salt.

9) The photographic film according to item 6), wherein the crosslinking agent is selected from the group consisting of polyfunctional aziridine, chromium alum, carbodiimide, and isoxazolinium salt.

10) The crosslinking agent is 0.0% based on the weight of the gelatin binder.
The photographic film according to item 5) above, wherein the film is present in an amount of 5 to 5% by weight.

11) The crosslinking agent is 0 based on the weight of the gelatin binder.
．． The photographic film according to item 6) above, which is present in a concentration of 5 to 5%.

12) The photographic film as described in the preceding item, wherein the crosslinkable conductive polymer is poly(sodium styrene sulfonate-maleic anhydride).

13) The photographic film described in 4) above, wherein the crosslinkable conductive polymer is poly(sodium styrene sulfonate-maleic anhydride rs).

14) The photographic film described in 7) above, wherein the crosslinking agent is a polyfunctional aziridine.

15) The photographic film described in 8) above, wherein the crosslinking agent is a polyfunctional aziridine.

16) The polyfunctional aziridine is pentaerythritol-trivator (2-methylaziridine), the preceding item 1
4) Photographic film as described.

17) The polyfunctional aziridine is pentaerythritol-trivator (2-methylaziridine), the preceding item 1
5) Photographic film as described.

1) The photographic film described in 1) above, wherein the support is a polyethylene terephthalate film.

19) The photographic film according to item 1) above, wherein the silver halide emulsion is covered with a protective overcoat layer.

20) a polyethylene terephthalate film support, at least one silver halide emulsion deposited on one side of the support, the emulsion layer covered by a protective overcoat layer, and on the opposite side of the support (a) a layer containing an antistatic agent and (b) an auxiliary layer are deposited in this order. A crosslinkable conductive polymer selected from the group consisting of dimethyl betaine, carboxylated imidazoline, cocoamido betaine, and mixtures thereof, and a multifunctional aziridine, chromium alum, carbodiimide, and isoxazolinium salt. a cross-linking agent selected from the group consisting of: dispersed in a gelatin binder, both of which are based on the weight of the seratin binder, and wherein the cross-linkable conductive polymer is 0.0. 5-30
% by weight and the crosslinking agent is present in an amount of 0.5 to 5 fi
A photographic film comprising 3 to 12 - deposits of 1% of J.

21) The photographic film according to item 20), wherein the auxiliary layer (b) is replaced by a crosslinkable conductive polymer/gelatin layer with a crosslinker/gelatin layer.

22) The photographic film according to item 20), wherein the crosslinkable conductive polymer is present in an amount of 1.5 to zsmm% based on the weight of the gelatin binder.

23) The crosslinking agent is 2 to 20% based on the weight of the gelatin binder.
The photographic film described in item 22) above, which exists as an external magnet with triple f%.

24) The crosslinkable conductive polymer is poly(sodium styrene sulfonate-maleic anhydride) and the crosslinker is pentaerythritol-trivator (24)
25) The crosslinkable conductive polymer is poly(sodium styrene sulfonate-maleic anhydride), and the crosslinking agent is pentaerythritol-tribate ( 2
-Methylaziridine), the photographic film O described in the preceding paragraph 21) and 2 other people

Claims (1)

[Scope of Claims] 1) consisting of a support, at least one silver halide emulsion deposited on one side of the support, and an antistatic agent deposited on the opposite side of the support, The antistatic layer consists essentially of at least one crosslinkable conductive polymer having functionally bonded carboxylic acid groups and a crosslinking agent for the conductive polymer dispersed in gelatin. Photographic film characterized in that an auxiliary layer is applied at a pH of 5 to 12, and the antistatic properties of the antistatic layer are derived through this auxiliary layer. 2) a polyethylene terephthalate film support, at least one silver halide emulsion deposited on one side of the support, the emulsion layer being covered by a protective overcoat layer, and the opposite side of the support (a) a layer containing an antistatic agent and (b) an auxiliary layer are deposited in this order, and the auxiliary layer consists of poly(sodium styrene sulfonate-maleic anhydride), hexadecyl betaine, alkyl A crosslinkable conductive polymer selected from the group consisting of dimethyl betaine, carboxylated imidazoline, cocoamido betaine, and mixtures thereof, and a multifunctional aziridine, chromium alum, carbodiimide, and isoxazolinium salt. a crosslinking agent selected from the group consisting of A photographic film comprising a crosslinking agent present in an amount of ~30% by weight and a crosslinking agent present in an amount of 0.5-5% by weight at a pH of 3-12.